JPH0742256B2 - Method for producing quaternary ammonium bicarbonate - Google Patents
Method for producing quaternary ammonium bicarbonateInfo
- Publication number
- JPH0742256B2 JPH0742256B2 JP27875586A JP27875586A JPH0742256B2 JP H0742256 B2 JPH0742256 B2 JP H0742256B2 JP 27875586 A JP27875586 A JP 27875586A JP 27875586 A JP27875586 A JP 27875586A JP H0742256 B2 JPH0742256 B2 JP H0742256B2
- Authority
- JP
- Japan
- Prior art keywords
- carbonate
- quaternary ammonium
- reaction
- tetramethylammonium
- bicarbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、第四級アンモニウム重炭酸塩の製造方法に関
する。TECHNICAL FIELD The present invention relates to a method for producing a quaternary ammonium bicarbonate.
第四級アンモニウム重炭酸塩は、界面活性剤として、ま
た界面活性剤の原料として広く使用されており、あるい
は医薬品、化粧品の原料としても有用なものである。The quaternary ammonium bicarbonate is widely used as a surfactant and a raw material for the surfactant, or is also useful as a raw material for pharmaceuticals and cosmetics.
近年、第四級アンモニウム重炭酸塩から誘導される第四
級アンモニウム水酸化物は電子工業、半導体産業におい
てIC、LSIなどの製造工程でウエハーの洗浄液、エッチ
ング液、現像液などへと多岐にわたり使用されている。In recent years, quaternary ammonium hydroxide derived from quaternary ammonium bicarbonate has been widely used as a cleaning solution for wafers, an etching solution, a developing solution in the manufacturing process of IC, LSI, etc. in the electronic industry and the semiconductor industry. Has been done.
本発明にかかる第四級アンモニウム重炭酸塩は、一般に
例えば（１）第四級アンモニウム水酸化物を炭酸化する
か、あるいは（２）第四級アンモニウムクロライドに炭
酸ガスとアンモニア水とを反応させることにより得るこ
とができる。The quaternary ammonium bicarbonate according to the present invention generally, for example, (1) carbonates quaternary ammonium hydroxide, or (2) causes quaternary ammonium chloride to react with carbon dioxide gas and aqueous ammonia. Can be obtained.
しかし、上記の（１）の方法は工業的には実用的でな
く、又（２）の方法は反応工程が煩雑でまた副生物が多
いなどの問題点がある。However, the above method (1) is not industrially practical, and the method (2) has problems that the reaction process is complicated and many by-products are produced.
本発明は、上記の現状に鑑み、純度の高い第四級アンモ
ニウム重炭酸塩を製造する方法を提供するにある。In view of the above situation, the present invention provides a method for producing a highly pure quaternary ammonium bicarbonate.
本発明者らは、上記した問題点を解決すべく種々の検討
を行った結果、第四級アンモニウムアルキルあるいはモ
ノアリール炭酸塩と水とを反応させることにより目的と
する第四級アンモニウム重炭酸塩を製造する方法を見出
した。The present inventors have conducted various studies to solve the above-mentioned problems, and as a result, made the target quaternary ammonium bicarbonate by reacting a quaternary ammonium alkyl or monoaryl carbonate with water. Have found a method of manufacturing.
すなわち、本発明は、第四級アンモニウムモノアルキル
あるいはモノアリール炭酸塩と水とを反応させることを
特徴とする第四級アンモニウム重炭酸塩の製造方法に関
する。That is, the present invention relates to a method for producing a quaternary ammonium bicarbonate, which comprises reacting a quaternary ammonium monoalkyl or monoaryl carbonate with water.
本発明の方法は下記式で表される。The method of the present invention is represented by the following formula.
本発明に用いられる第四級アンモニウムモノアルキルあ
るいはモノアリール炭酸塩は一般式 で表される（式中、R1,R2,R3はC1〜C8のアルキル基、ア
ルケニル基、フェニル基、ベンジル基を示し、式中R4,R
5はC1〜C8のアルキル基またはアリール基を示す）。具
体的には、テトラメチルアンモニウム−メチル炭酸塩、
テトラメチルアンモニウム−エチル炭酸塩、テトラメチ
ルアンモニウム−イソプロピル炭酸塩、テトラメチルア
ンモニウム−ｎ−ブチル炭酸塩、テトラメチルアンモニ
ウム−フェニル炭酸塩、テトラメチルアンモニウム−ベ
ンジル炭酸塩、テトラエチルアンモニウム−メチル炭酸
塩、テトラエチルアンモニウム−エチル炭酸塩、テトラ
プロピルアンモニウム−メチル炭酸塩、テトラブチルア
ンモニウム−メチル炭酸塩、トリメチルエチルアンモニ
ウム−メチル炭酸塩、トリメチルプロピルアンモニウム
−メチル炭酸塩、トリメチルプロピルアンモニウム−プ
ロピル炭酸塩、トリメチルベンジルアンモニウム−メチ
ル炭酸塩、トリメチルヒドロキシエチルアンモニウム−
メチル炭酸塩、トリメチルメトキシエチルアンモニウム
−メチル炭酸塩、トリメチルエチルアンモニウム−ベン
ジル炭酸塩、ジメチルジエチルアンモニウム−メチル炭
酸塩、等が例示される。 The quaternary ammonium monoalkyl or monoaryl carbonate used in the present invention has the general formula In in represented by (wherein, R 1, R 2, R 3 represents an alkyl group of C 1 -C 8, an alkenyl group, a phenyl group, a benzyl group, wherein R 4, R
5 represents a C 1 -C 8 alkyl group or aryl group). Specifically, tetramethylammonium-methyl carbonate,
Tetramethylammonium-ethyl carbonate, tetramethylammonium-isopropyl carbonate, tetramethylammonium-n-butyl carbonate, tetramethylammonium-phenyl carbonate, tetramethylammonium-benzyl carbonate, tetraethylammonium-methylcarbonate, tetraethyl Ammonium-ethyl carbonate, tetrapropyl ammonium-methyl carbonate, tetrabutyl ammonium-methyl carbonate, trimethyl ethyl ammonium-methyl carbonate, trimethyl propyl ammonium-methyl carbonate, trimethyl propyl ammonium-propyl carbonate, trimethyl benzyl ammonium- Methyl carbonate, trimethyl hydroxyethyl ammonium-
Examples include methyl carbonate, trimethylmethoxyethyl ammonium-methyl carbonate, trimethylethyl ammonium-benzyl carbonate, dimethyl diethyl ammonium-methyl carbonate, and the like.
この様な第四級アンモニウムモノアルキル炭酸塩あるい
はモノアリール炭酸塩は、例えば、米国特許第2635100
号に示されるように、アルコール等の極性溶媒の存在下
または非存在下に炭酸ジアルキルあるいは炭酸ジアリー
ルと第三級アミンとを反応させることにより容易に得る
ことができる。Such quaternary ammonium monoalkyl carbonates or monoaryl carbonates are described, for example, in US Pat.
As shown in No. 4, it can be easily obtained by reacting a dialkyl carbonate or diaryl carbonate with a tertiary amine in the presence or absence of a polar solvent such as alcohol.
本発明において、水は反応原料であると共に、反応溶媒
として作用するので、一般的に使用する第四級アンモニ
ウムアルキル炭酸塩あるいはモノアリール炭酸塩に対し
て理論量以上使用され、好ましくは２〜30倍（モル）で
ある。従って水は過剰に使用されるが、余りにも多量で
あると反応後の分離、除去に時間を要するので得策でな
い。本発明の方法においては、アルコール類、ニトリル
類、酸アミド類等の極性溶媒を使用することができる。
極性溶媒を使用することにより、反応初期の反応速度を
高めることができ全体の反応を短時間に行うことができ
る。さらに反応収率を高める効果もある。In the present invention, since water is a reaction raw material and acts as a reaction solvent, it is used in a theoretical amount or more with respect to a commonly used quaternary ammonium alkyl carbonate or monoaryl carbonate, preferably 2 to 30. It is twice (mol). Therefore, water is used in excess, but if it is too large, it takes time to separate and remove it after the reaction, which is not a good idea. In the method of the present invention, polar solvents such as alcohols, nitriles and acid amides can be used.
By using a polar solvent, the reaction rate at the initial stage of the reaction can be increased and the entire reaction can be carried out in a short time. It also has the effect of increasing the reaction yield.
この様な極性溶媒としては、例えば、メタノール、エタ
ノール、プロパノール、等の脂肪族低級アルコール類、
ベンアルアルコールの様な一価芳香族アルコール、エチ
レングリコールの様なグリコール類、N,N−ジメチルホ
ルムアミドの様な酸アミド類、アセトニトリルの様なニ
トリル類が例示されるが、これら極性溶媒はその沸点が
余り高くないものが好ましく、沸点50〜200℃の範囲に
あるものがよく、好ましくはメタノール、エタノール、
プロパノール、アセトニトリル等が反応後の分離操作な
どの点から好適である。Examples of such a polar solvent include aliphatic lower alcohols such as methanol, ethanol, propanol, and the like,
Monohydric aromatic alcohols such as benzyl alcohol, glycols such as ethylene glycol, acid amides such as N, N-dimethylformamide, and nitriles such as acetonitrile are exemplified, but these polar solvents are It is preferable that the boiling point is not too high, and it is preferable that the boiling point is in the range of 50 to 200 ° C., preferably methanol, ethanol,
Propanol, acetonitrile and the like are preferable from the viewpoint of separation operation after the reaction.
これら極性溶媒の使用量は原料第四級アンモニウムモノ
アルキル炭酸塩あるいはモノアリール炭酸塩に対して0.
5〜30倍量（重量）であり、通常は１〜20倍量、好まし
くは２〜10倍量が使用される 本発明の方法を実施する際の反応温度は、一般的には30
〜300℃の範囲であるが、実際には反応速度、原料の第
四級アンモニウムモノアルキル炭酸塩あるいはモノアリ
ール炭酸塩および目的物の第四級アンモニウム重炭酸塩
の分解等を考慮する必要があり、通常は40〜250℃好ま
しくは50〜200℃である。The amount of these polar solvents to be used is 0 with respect to the raw material quaternary ammonium monoalkyl carbonate or monoaryl carbonate.
5 to 30 times amount (weight), usually 1 to 20 times amount, preferably 2 to 10 times amount is used. When carrying out the method of the present invention, the reaction temperature is generally 30.
Although it is in the range of up to 300 ° C, it is necessary to consider the reaction rate, the decomposition of the quaternary ammonium monoalkyl carbonate or monoaryl carbonate as the raw material and the quaternary ammonium bicarbonate as the target substance. The temperature is usually 40 to 250 ° C, preferably 50 to 200 ° C.
なお、本発明は、必要に応じて、窒素、アルゴンヘリウ
ム、あるいは水素ガス等の反応に影響を与えない不活性
ガス雰囲気下で反応させることもできる。又、本発明は
回分式、半回分式あるいは連続式何れの方法でも実施し
得る。In the present invention, the reaction may be carried out under an inert gas atmosphere that does not affect the reaction of nitrogen, argon helium, hydrogen gas or the like, if necessary. Further, the present invention can be carried out by any of batch, semi-batch and continuous methods.
本発明は、炭酸ジアルキルあるいは炭酸ジアリールと第
三級アミンとから得られる第四級アンモニウムモノアル
キル炭酸塩あるいはモノアリール炭酸塩と水とを反応さ
せることにより第四級アンモニウム重炭酸塩の製造を高
収率で行うことができる新規な方法でり、工業的にきわ
めて有意義な方法である。The present invention enhances the production of quaternary ammonium bicarbonate by reacting water with a quaternary ammonium monoalkyl carbonate or monoaryl carbonate obtained from a dialkyl carbonate or diaryl carbonate and a tertiary amine. It is a novel method that can be carried out in yield, and is an industrially very meaningful method.
以下に本発明の実施例を示す。Examples of the present invention will be shown below.
実施例 １ 300mlの内容積のオートクレーブに、テトラメチルアン
モニウムモノメチル炭酸塩108.0g、水72.0g、を導入
し、加熱、撹拌した。反応器内の温度が100℃に達した
後その温度で３時間反応を継続させた。反応終了後、生
成物を分析した結果、テトラメチルアンモニウム重炭酸
塩が96.7％（モル）の収率で得られた。Example 1 Tetramethylammonium monomethyl carbonate (108.0 g) and water (72.0 g) were introduced into an autoclave having an inner volume of 300 ml, and the mixture was heated and stirred. After the temperature in the reactor reached 100 ° C, the reaction was continued at that temperature for 3 hours. After the reaction was completed, the product was analyzed and as a result, tetramethylammonium bicarbonate was obtained in a yield of 96.7% (mol).
実施例 ２ 実施例１で使用したと同様の反応器に、テトラメチルア
ンモニウムモメチル炭酸塩86.4g、水93.6g、を導入し、
加熱撹拌した。反応器内の温度が100℃に達した後その
温度で３時間反応を継続させた。反応終了後、生成物を
分析した結果、テトラメチルアンモニウム重炭酸塩が9
7.1％（モル）の収率で得られた。Example 2 86.4 g of tetramethylammonium momethyl carbonate and 93.6 g of water were introduced into a reactor similar to that used in Example 1,
Heated and stirred. After the temperature in the reactor reached 100 ° C, the reaction was continued at that temperature for 3 hours. After the reaction was completed, the product was analyzed and found to contain 9% tetramethylammonium bicarbonate.
Obtained in a yield of 7.1% (mol).
実施例 ３ 実施例１で使用したと同様の反応器に、テトラメチルア
ンモニウムモメチル炭酸塩108.0g、水72.0g、メタノー
ル32.0gを導入し、加熱撹拌した。反応器内の温度が100
℃に達した後その温度で３時間反応を継続させた。反応
終了後、生成物を分析した結果、テトラメチルアンモニ
ウム重炭酸塩が98.5％（モル）の収率で得られた。Example 3 Tetramethylammonium momethyl carbonate (108.0 g), water (72.0 g) and methanol (32.0 g) were introduced into the same reactor as that used in Example 1, and the mixture was heated and stirred. The temperature inside the reactor is 100
After reaching ℃, the reaction was continued at that temperature for 3 hours. After the reaction was completed, the product was analyzed and as a result, tetramethylammonium bicarbonate was obtained in a yield of 98.5% (mol).
実施例 ４ 実施例１で使用したと同様の反応器に、トリメチルエチ
ルアンモニウムモメチル炭酸塩114.1g,水75.6g、を導入
し、加熱撹拌した。反応器内の温度が120℃に達した後
その温度で３時間反応を継続させた。反応終了後、生成
物を分析した結果トリメチルエチルアンモニウム重炭酸
塩が96.3％（モル）の収率で得られた。Example 4 114.1 g of trimethylethylammonium momethyl carbonate and 75.6 g of water were introduced into the same reactor as used in Example 1 and stirred with heating. After the temperature in the reactor reached 120 ° C, the reaction was continued at that temperature for 3 hours. After the reaction was completed, the product was analyzed and trimethylethylammonium bicarbonate was obtained in a yield of 96.3% (mol).
実施例 ５ 実施例１で使用したと同様の反応器に、テトラメチルア
ンモニウム−イソプロピル炭酸塩88.5g水45.0g、を導入
し、加熱撹拌した。反応器内の温度が120℃に達した後
その温度で３時間反応を継続させた。反応終了後、生成
物を分析した結果テトラメチルアンモニウム重炭酸塩が
95.0％（モル）の収率で得られた。Example 5 Tetramethylammonium-isopropyl carbonate 88.5 g water 45.0 g was introduced into the same reactor as used in Example 1, and the mixture was heated and stirred. After the temperature in the reactor reached 120 ° C, the reaction was continued at that temperature for 3 hours. After the reaction was completed, analysis of the product revealed that tetramethylammonium bicarbonate had
Obtained in a yield of 95.0% (mol).
実施例 ６ 実施例１で使用したと同様の反応器に、トリメチルベン
ジルアンモニウムモメチル炭酸塩112.5g,水55.0g、を導
入し、加熱撹拌した。反応器内の温度が120℃に達した
後その温度で３時間反応を継続させた。反応終了後、生
成物を分析した結果トリメチルベンジルアンモニウム重
炭酸塩が95.7％（モル）の収率で得られた。Example 6 To the same reactor as used in Example 1, trimethylbenzylammonium momethyl carbonate (112.5 g) and water (55.0 g) were introduced, and the mixture was heated and stirred. After the temperature in the reactor reached 120 ° C, the reaction was continued at that temperature for 3 hours. After the reaction was completed, the product was analyzed and trimethylbenzylammonium bicarbonate was obtained in a yield of 95.7% (mol).
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 米国特許2635100（ＵＳ，Ａ) ─────────────────────────────────────────────────── ─── Continued Front Page (56) References US Patent 2635100 (US, A)
Claims (1)
モノアリール炭酸塩と水とを反応させることを特徴とす
る第四級アンモニウム重炭酸塩の製造方法1. A method for producing a quaternary ammonium bicarbonate, which comprises reacting a quaternary ammonium monoalkyl or monoaryl carbonate with water.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27875586A JPH0742256B2 (en) | 1986-11-25 | 1986-11-25 | Method for producing quaternary ammonium bicarbonate |
| US07/120,150 US4776929A (en) | 1986-11-25 | 1987-11-12 | Process for production of quaternary ammonium hydroxides |
| DE87117020T DE3785548T2 (en) | 1986-11-25 | 1987-11-18 | Process for the production of a high-purity quaternary ammonium hydroxide. |
| EP87117020A EP0269949B1 (en) | 1986-11-25 | 1987-11-18 | Process for producing a high purity quaternary ammonium hydroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27875586A JPH0742256B2 (en) | 1986-11-25 | 1986-11-25 | Method for producing quaternary ammonium bicarbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63132863A JPS63132863A (en) | 1988-06-04 |
| JPH0742256B2 true JPH0742256B2 (en) | 1995-05-10 |
Family
ID=17601743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27875586A Expired - Lifetime JPH0742256B2 (en) | 1986-11-25 | 1986-11-25 | Method for producing quaternary ammonium bicarbonate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0742256B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005029715A (en) * | 2003-07-08 | 2005-02-03 | National Institute Of Advanced Industrial & Technology | Method for producing bio-diesel fuel |
| US7928184B2 (en) | 2005-03-15 | 2011-04-19 | Polyplastics Co., Ltd. | Unstable terminal group decomposer, and stabilized polyacetal resin, manufacturing method, composition and molded article using the same |
-
1986
- 1986-11-25 JP JP27875586A patent/JPH0742256B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63132863A (en) | 1988-06-04 |
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